CN111086985B - Preparation method of graphene carbon nanotube composite aerogel electrode material - Google Patents
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 137
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 92
- 239000004964 aerogel Substances 0.000 title claims abstract description 38
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 38
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 38
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 239000007772 electrode material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000002109 single walled nanotube Substances 0.000 claims abstract description 78
- 239000006185 dispersion Substances 0.000 claims abstract description 51
- 239000007788 liquid Substances 0.000 claims abstract description 38
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 36
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 36
- 239000002608 ionic liquid Substances 0.000 claims abstract description 26
- 238000001035 drying Methods 0.000 claims abstract description 24
- 238000000967 suction filtration Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000007710 freezing Methods 0.000 claims abstract description 10
- 230000008014 freezing Effects 0.000 claims abstract description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 8
- 238000005342 ion exchange Methods 0.000 claims abstract description 8
- 238000000746 purification Methods 0.000 claims abstract description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 30
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000000047 product Substances 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 25
- 239000006228 supernatant Substances 0.000 claims description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 21
- 239000012153 distilled water Substances 0.000 claims description 18
- 238000001291 vacuum drying Methods 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 15
- 125000002883 imidazolyl group Chemical group 0.000 claims description 14
- 239000012528 membrane Substances 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 11
- 239000011541 reaction mixture Substances 0.000 claims description 11
- 238000003760 magnetic stirring Methods 0.000 claims description 10
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 9
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- 239000012043 crude product Substances 0.000 claims description 7
- 239000012065 filter cake Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 239000012286 potassium permanganate Substances 0.000 claims description 7
- 239000012264 purified product Substances 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 239000013049 sediment Substances 0.000 claims description 7
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 claims description 5
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 claims description 4
- MYMSJFSOOQERIO-UHFFFAOYSA-N 1-bromodecane Chemical compound CCCCCCCCCCBr MYMSJFSOOQERIO-UHFFFAOYSA-N 0.000 claims description 3
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 abstract 3
- 238000002474 experimental method Methods 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 9
- KYCQOKLOSUBEJK-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;bromide Chemical compound [Br-].CCCCN1C=C[N+](C)=C1 KYCQOKLOSUBEJK-UHFFFAOYSA-M 0.000 description 7
- 238000002329 infrared spectrum Methods 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 238000001237 Raman spectrum Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 2
- RVEJOWGVUQQIIZ-UHFFFAOYSA-N 1-hexyl-3-methylimidazolium Chemical compound CCCCCCN1C=C[N+](C)=C1 RVEJOWGVUQQIIZ-UHFFFAOYSA-N 0.000 description 2
- WXMVWUBWIHZLMQ-UHFFFAOYSA-N 3-methyl-1-octylimidazolium Chemical compound CCCCCCCCN1C=C[N+](C)=C1 WXMVWUBWIHZLMQ-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical class CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical class CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical class CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- BGSUDDILQRFOKZ-UHFFFAOYSA-M 1-hexyl-3-methylimidazol-3-ium;bromide Chemical compound [Br-].CCCCCCN1C=C[N+](C)=C1 BGSUDDILQRFOKZ-UHFFFAOYSA-M 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
- C01B32/166—Preparation in liquid phase
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Abstract
A preparation method of a graphene carbon nanotube composite aerogel electrode material belongs to the field of new energy material preparation, and relates to preparation of a carbon nanotube composite material. The invention aims to solve the technical problems of poor thermal stability and low electrical conductivity of graphene carbon nanotube aerogel prepared by the existing method. The method comprises the following steps: firstly, preparing ionic liquid; secondly, preparing graphene oxide; thirdly, preparing the oxidized single-walled carbon nanotube; and fourthly, respectively placing the graphene oxide and the oxidized single-walled carbon nanotube into imidazole-based ionic liquid for ultrasonic crushing and dispersion, adding the graphene oxide dispersion liquid and the oxidized single-walled carbon nanotube dispersion liquid with equal volumes into the PTFE liner, adjusting the pH value of the mixed liquid to 8-13 by using ammonia water with concentration, drying, performing ion exchange purification, suction filtration and freezing to obtain the graphene oxide/single-walled carbon nanotube composite material. The composite electrode material prepared by the invention has good plasticity, thermal stability and conductivity, and has high specific surface area and excellent electrochemical properties.
Description
Technical Field
The invention belongs to the field of preparation of new energy materials, and particularly relates to a preparation method of a graphene carbon nanotube composite material.
Background
The graphene and carbon nanotube aerogel has good elastic properties and is particularly suitable for preparing electrode materials of flexible batteries. The graphene carbon nanotube aerogel composite material can be used as an electrode material of a lithium ion battery to construct a flexible lithium ion battery. The electrochemical stability of the battery is improved to a great extent on the premise of ensuring the normal operation of the battery by fully utilizing the characteristics of two-dimensional pore channels, high conductivity, high surface functionalization, lightness, thinness, easiness in processing, certain mechanical strength, optical characteristics, easiness in loading more active components and the like. Patent document No. CN109824037A discloses a method for preparing a graphene aerogel electrode material. The preparation process of the ionic liquid is rough, the product is impure, and it is difficult to indicate which component in the prepared ionic liquid plays a due role in the gelling process. And the graphene is not dispersed in place, so that the aerogel with uniform structure and uniform gaps is difficult to form. The relevant electrochemical property characterization diagram of the graphene electrode is not seen, and the outstanding advantages of the electrode and the advantages of the electrode over other preparation methods are difficult to explain.
At present, most of graphene carbon nanotube aerogel preparation methods are self-assembly and transfer methods, and a hydrothermal method is less. The operation difficulty and the uncontrollable property of the former two methods can cause poor thermal stability, low conductivity, higher production cost and low yield of the electrode material, and the electrode material cannot meet the basic requirements of green chemistry.
Disclosure of Invention
The invention aims to solve the technical problems of poor thermal stability and low conductivity of graphene carbon nanotube aerogel prepared by the existing method, and provides a preparation method of a graphene carbon nanotube composite aerogel electrode material.
The preparation method of the graphene carbon nanotube composite aerogel electrode material comprises the following steps:
mixing 1-bromo-N-alkane or bromo-alkane with N-methylimidazole, magnetically stirring for 24 hours at 60 ℃ in an oil bath, pouring out supernatant, adding ethyl acetate into the generated viscous product for washing, fully stirring, pouring out supernatant, adding acetonitrile into the washed crude product, heating to dissolve an intermediate, repeating the washing steps until a clear and transparent viscous product is obtained, and placing the viscous product in a vacuum drying oven at 60 ℃ for drying for 24 hours to obtain imidazolyl ionic liquid;
wherein the mass ratio of the N-methylimidazole, the 1-bromo-N-alkane, the acetonitrile and the ethyl acetate is 1-5: 5-10: any;
secondly, 5-10 g of KMnO4Gradually adding 50-100 mL of concentrated H cooled in an ice bath2SO4And 1-10 g of graphite flakes, then magnetically stirring for 0.5-1 h at 50 ℃, slowly adding 50-100 mL of distilled water, and stirring the mixture for 10-30 minutes at 95 ℃;
thirdly, sequentially adding 200-300 mL of distilled water and 10-30 mL of H with the mass fraction of 30% into the product obtained in the second step2O2Centrifuging the reaction mixture at the speed of 5000 rpm, dispersing the centrifuged sediment in 300-500 mL of HCl with the mass fraction of 10%, and centrifuging the dispersion;
fourthly, repeating the third step for 3 times until the pH value of the supernatant is 5-7, and then collecting the graphene oxide from a centrifugal machine and drying the graphene oxide in vacuum at the temperature of 60 ℃ to obtain the graphene oxide;
fifthly, oxidizing the single-walled carbon nanotube in 400 ℃ air atmosphere for 2h in sequence, then acidifying the single-walled carbon nanotube for 24h by using concentrated hydrochloric acid to obtain a primary purified product of SWNTs, taking 100-200 mg of the primarily purified SWNTs, adding 150-200 mL of potassium peroxodisulfate solution with the concentration of 0.2mol/L, ultrasonically crushing and dispersing for 1-2 h at 10 ℃, adding 12.5-15 mL of concentrated sulfuric acid with the mass fraction of 97% into the reaction system, placing the reaction system in an oil bath at 60 ℃ for magnetic stirring and refluxing for 24-36 h, after the reaction is finished, removing the upper yellow solution after the system is cooled, pouring and dispersing the lower black component for multiple times until a stable suspension is formed, finally performing suction filtration on the suspension by using a 1 micron PTFE filter membrane, and placing the obtained filter cake in vacuum drying for 8h at 100 ℃ to obtain the oxidized single-walled carbon nanotube;
sixthly, respectively taking 1mg of graphene oxide and the oxidized single-walled carbon nanotube, respectively placing the graphene oxide and the oxidized single-walled carbon nanotube into 100mL of imidazolyl ionic liquid with the mass fraction of 1-2%, and performing ultrasonic crushing and dispersion to respectively obtain a graphene oxide dispersion liquid and a dispersion liquid of the oxidized single-walled carbon nanotube;
and seventhly, adding the equal-volume graphene oxide dispersion liquid and the dispersion liquid of the oxidized single-walled carbon nanotube into the PTFE liner, adjusting the pH value of the mixed liquid to 8-13 by using dilute ammonia water with the concentration of 2-5 mol/L, putting the PTFE liner into a reaction kettle, screwing down, putting the PTFE liner into a blast drying oven, drying for 1-24 hours at the temperature of 60 ℃, then putting the PTFE liner into a semipermeable membrane for ion exchange purification and suction filtration, and freezing for 36-48 hours at the temperature of-25 ℃ to obtain the graphene carbon nanotube aerogel composite material.
In the step one, the 1-bromo n-alkane is 1-bromo-n-ethane, 1-bromo-n-butane, 1-bromo-n-hexane, 1-bromo-n-octane or 1-bromo-n-decane;
in the step one, the brominated alkanes are 2-brominated n-butane, 2-brominated n-hexane, 2-brominated n-octane and 2-brominated n-decane.
Concentrated H as described in step two2SO4The concentration is 98%, 80%, 70%, 60% or 50%.
The composite electrode material prepared by the invention has good plasticity, thermal stability and conductivity, and has high specific surface area and excellent electrochemical properties; the mechanical strength of the prepared composite material can be increased to a great extent by compounding the one-dimensional single-walled carbon nanotube and the two-dimensional graphene sheet layer, and the electron flow rate on the surface can be increased after oxidation.
Drawings
FIG. 1 is a representation of the infrared spectra of ionic liquids prepared in experiments one to four;
FIG. 2 is a Raman spectrum characterization chart of a single-walled carbon nanotube before and after oxidation in the first experiment, wherein 1 shows the Raman spectrum characterization chart of the single-walled carbon nanotube before oxidation, and 2 shows the Raman spectrum characterization chart of the single-walled carbon nanotube after oxidation;
FIG. 3 is a diagram of the ultraviolet-visible near-infrared spectra of single-walled carbon nanotubes dispersed in ionic liquid aqueous solution prepared in experiments one to four, wherein a represents the ultraviolet-visible near-infrared spectra of single-walled carbon nanotubes dispersed in [ EMIM ] Br ionic liquid aqueous solution, b represents the ultraviolet-visible near-infrared spectra of single-walled carbon nanotubes dispersed in [ BMIM ] Br ionic liquid aqueous solution, c represents the ultraviolet-visible near-infrared spectra of single-walled carbon nanotubes dispersed in [ HMIM ] Br ionic liquid aqueous solution, and d represents the ultraviolet-visible near-infrared spectra of single-walled carbon nanotubes dispersed in [ OMIM ] Br ionic liquid aqueous solution;
FIG. 4 is a CV curve of a graphene carbon nanotube composite aerogel electrode prepared by using a [ BMIM ] Br aqueous solution as a dispersant in the first experiment;
FIG. 5 is a GCD curve of a graphene carbon nanotube composite aerogel electrode prepared by taking a [ BMIM ] Br aqueous solution as a dispersant in the first experiment;
FIG. 6 is a specific capacitance curve of a graphene carbon nanotube composite aerogel electrode prepared by taking a [ BMIM ] Br aqueous solution as a dispersant in the first experiment at different current densities;
fig. 7 is a cycle number curve of the graphene carbon nanotube composite aerogel electrode prepared by using a [ BMIM ] Br aqueous solution as a dispersant in the first experiment under different current densities.
Detailed Description
The technical solution of the present invention is not limited to the following specific embodiments, but includes any combination of the specific embodiments.
The first embodiment is as follows: the preparation method of the graphene carbon nanotube composite aerogel electrode material of the embodiment is as follows:
mixing 1-bromo-N-alkane or bromo-alkane with N-methylimidazole, magnetically stirring for 24 hours at 60 ℃ in an oil bath, pouring out supernatant, adding ethyl acetate into the generated viscous product for washing, fully stirring, pouring out supernatant, adding acetonitrile into the washed crude product, heating to dissolve an intermediate, repeating the washing steps until a clear and transparent viscous product is obtained, and placing the viscous product in a vacuum drying oven at 60 ℃ for drying for 24 hours to obtain imidazolyl ionic liquid;
wherein the mass ratio of the N-methylimidazole, the 1-bromo-N-alkane, the acetonitrile and the ethyl acetate is 1-5: 5-10: any;
secondly, 5-10 g of KMnO4Gradually adding 50-100 mL of concentrated H cooled in an ice bath2SO4And 1-10 g of graphite flakes, then magnetically stirring for 0.5-1 h at 50 ℃, slowly adding 50-100 mL of distilled water, and stirring the mixture for 10-30 minutes at 95 ℃;
thirdly, sequentially adding 200-300 mL of distilled water and 10-30 mL of H with the mass fraction of 30% into the product obtained in the second step2O2Centrifuging the reaction mixture at the speed of 5000 rpm, dispersing the centrifuged sediment in 300-500 mL of HCl with the mass fraction of 10%, and centrifuging the dispersion;
fourthly, repeating the third step for 3 times until the pH value of the supernatant is 5-7, and then collecting the graphene oxide from a centrifugal machine and drying the graphene oxide in vacuum at the temperature of 60 ℃ to obtain the graphene oxide;
fifthly, oxidizing the single-walled carbon nanotube in 400 ℃ air atmosphere for 2h in sequence, then acidifying the single-walled carbon nanotube for 24h by using concentrated hydrochloric acid to obtain a primary purified product of SWNTs, taking 100-200 mg of the primarily purified SWNTs, adding 150-200 mL of potassium peroxodisulfate solution with the concentration of 0.2mol/L, ultrasonically crushing and dispersing for 1-2 h at 10 ℃, adding 12.5-15 mL of concentrated sulfuric acid with the mass fraction of 97% into the reaction system, placing the reaction system in an oil bath at 60 ℃ for magnetic stirring and refluxing for 24-36 h, after the reaction is finished, removing the upper yellow solution after the system is cooled, pouring and dispersing the lower black component for multiple times until a stable suspension is formed, finally performing suction filtration on the suspension by using a 1 micron PTFE filter membrane, and placing the obtained filter cake in vacuum drying for 8h at 100 ℃ to obtain the oxidized single-walled carbon nanotube;
sixthly, respectively taking 1mg of graphene oxide and the oxidized single-walled carbon nanotube, respectively placing the graphene oxide and the oxidized single-walled carbon nanotube into 100mL of imidazolyl ionic liquid with the mass fraction of 1-2%, and performing ultrasonic crushing and dispersion to respectively obtain a graphene oxide dispersion liquid and a dispersion liquid of the oxidized single-walled carbon nanotube;
and seventhly, adding the equal-volume graphene oxide dispersion liquid and the dispersion liquid of the oxidized single-walled carbon nanotube into the PTFE liner, adjusting the pH value of the mixed liquid to 8-13 by using dilute ammonia water with the concentration of 2-5 mol/L, putting the PTFE liner into a reaction kettle, screwing down, putting the PTFE liner into a blast drying oven, drying for 1-24 hours at the temperature of 60 ℃, then putting the PTFE liner into a semipermeable membrane for ion exchange purification and suction filtration, and freezing for 36-48 hours at the temperature of-25 ℃ to obtain the graphene carbon nanotube aerogel composite material.
The second embodiment is as follows: the difference between the first embodiment and the second embodiment is that the 1-bromo n-alkane in the first step is 1-bromo n-ethane, 1-bromo n-butane, 1-bromo n-hexane, 1-bromo n-octane or 1-bromo n-decane; in the step one, the brominated alkane is 2-brominated n-butane, 2-brominated n-hexane, 2-brominated n-octane or 2-brominated n-decane. The rest is the same as the first embodiment.
The third concrete implementation mode: this embodiment differs from the first or second embodiment in that the concentration of H in the second step2SO4The concentration is 98 percent and 80 percent,70%, 60% or 50%. The others are the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment and the first to third embodiments is that in the second step, 6-8 g KMnO is used4Gradually adding the mixture into 60-80 mL of concentrated H cooled in an ice bath2SO4And 2-4 g of graphite flakes. The rest is the same as one of the first to third embodiments.
The fifth concrete implementation mode: the difference between the second embodiment and the first to the fourth embodiment is that in the second step, the mixture is stirred for 15 to 25 minutes at 95 ℃, 200 to 300 mL of distilled water and 15 to 25 mL of H with the mass fraction of 30% are sequentially added2O2Thereafter, the reaction mixture was centrifuged at 5000 rpm. The rest is the same as one of the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is that in the second step, the mixture is stirred at 95 ℃ for 20 minutes, 200 to 300 mL of distilled water and 20 mL of H with a mass fraction of 30% are added in this order2O2Thereafter, the reaction mixture was centrifuged at 5000 rpm. The rest is the same as one of the first to fifth embodiments.
The seventh embodiment: this embodiment differs from one of the first to sixth embodiments in that the supernatant in step four has a pH of 6. The rest is the same as one of the first to sixth embodiments.
The specific implementation mode is eight: the difference between the first embodiment and the seventh embodiment is that 150mg of primarily purified SWNTs are taken in the fifth step, 160mL of potassium peroxodisulfate solution with the concentration of 0.2mol/L is added, ultrasonic crushing and dispersion are carried out for 1-2 h at 10 ℃, and 13mL of concentrated sulfuric acid with the mass fraction of 97% is added into the reaction system. The rest is the same as one of the first to seventh embodiments.
The specific implementation method nine: the difference between this embodiment and the first to eighth embodiments is that step seven adjusts the pH of the mixture to 10. The rest is the same as the first to eighth embodiments.
The detailed implementation mode is ten: this embodiment differs from one of the first to ninth embodiments in that in step seven the freezing is carried out at-25 ℃ for 40 h. The rest is the same as one of the first to ninth embodiments.
The following experiments are adopted to verify the effect of the invention:
experiment one:
the preparation method of the graphene carbon nanotube composite aerogel electrode material comprises the following steps:
mixing 1-bromon-butane and N-methylimidazole (fractionating the N-methylimidazole and the 1-bromon-butane, drying and removing residual water in a sample) according to the mass ratio of 1: 2, magnetically stirring for 24 hours under a 60 ℃ oil bath, pouring out supernatant, adding ethyl acetate into the generated viscous product for washing, fully stirring and then pouring out the supernatant, adding acetonitrile into the washed crude product, heating to dissolve an intermediate, repeating the washing steps until a clear and transparent viscous product is obtained, and placing the viscous product in a vacuum drying oven at 60 ℃ for drying for 24 hours to obtain imidazolyl ionic liquid (1-N-butyl-3-methylimidazolium bromide ionic liquid [ BMIM ] Br), wherein the yield is about 85%;
secondly, 10g of KMnO4Gradually added to 100mL of concentrated H cooled in an ice bath2SO4And 10g of graphite flakes (to maintain the temperature within the range of 0-10 ℃), then magnetically stirring at 50 ℃ for 1h, slowly adding 80 mL of distilled water, and stirring the mixture at 95 ℃ for another 30 minutes;
thirdly, adding 300 mL of distilled water and 30 mL of H with the mass fraction of 30% into the product obtained in the second step in sequence2O2Then, the reaction mixture was centrifuged at 5000 rpm, and the centrifuged sediment was dispersed in 500mL of HCl having a mass fraction of 10%, and then the dispersion was centrifuged;
fourthly, repeating the third step for 3 times until the pH value of the supernatant is 5, and then collecting the graphene oxide from a centrifugal machine and drying the graphene oxide in vacuum at the temperature of 60 ℃ to obtain the graphene oxide;
fifthly, oxidizing the single-walled carbon nanotube in 400 ℃ air atmosphere for 2h in sequence, then acidifying the single-walled carbon nanotube for 24h by using concentrated hydrochloric acid to obtain a primary purified product of SWNTs, putting 150mg of the primarily purified SWNTs into a 250mL plastic beaker, adding 200mL of potassium peroxodisulfate solution with the concentration of 0.2mol/L, performing ultrasonic crushing and dispersion for 2h at 10 ℃, adding 15mL of concentrated sulfuric acid with the mass fraction of 97% into the reaction system, placing the reaction system in an oil bath at 60 ℃ for magnetic stirring and refluxing for 36h, ending the reaction, removing an upper yellow solution after the system is cooled, pouring and dispersing a lower black component for multiple times until a stable suspension is formed, finally performing suction filtration on the suspension by using a 1 micron PTFE filter membrane, and placing the obtained filter cake in a 100 ℃ for vacuum drying for 8h to obtain the oxidized single-walled carbon nanotube;
sixthly, respectively taking 1mg of graphene oxide and the oxidized single-walled carbon nanotube, respectively placing the graphene oxide and the oxidized single-walled carbon nanotube into 100mL of imidazolyl ionic liquid with the mass fraction of 1%, and performing ultrasonic crushing and dispersion to respectively obtain a graphene oxide dispersion liquid and a dispersion liquid of the oxidized single-walled carbon nanotube;
and seventhly, adding the equal-volume graphene oxide dispersion liquid and the dispersion liquid of the oxidized single-walled carbon nanotube into the PTFE liner, adjusting the pH value of the mixed liquid to 10 by using dilute ammonia water with the concentration of 2mol/L, then putting the PTFE liner into a reaction kettle to be screwed tightly, putting the PTFE liner into a forced air drying oven to be dried for 24 hours at the temperature of 60 ℃, then putting the PTFE liner into a semipermeable membrane to carry out ion exchange purification, carrying out suction filtration, and freezing for 48 hours at the temperature of-25 ℃ in a vacuum drying oven to obtain the graphene carbon nanotube aerogel composite material.
Experiment two:
the preparation method of the graphene carbon nanotube composite aerogel electrode material comprises the following steps:
firstly, mixing 1-bromobelt N-hexane and N-methylimidazole according to the mass ratio of 1: 2, magnetically stirring for 24 hours under a 60 ℃ oil bath, pouring out supernatant, adding ethyl acetate into the generated viscous product for washing, fully stirring, pouring out supernatant, adding acetonitrile into the washed crude product, heating to dissolve an intermediate, repeating the washing steps until a clear and transparent viscous product is obtained, and placing the viscous product in a 60 ℃ vacuum drying oven for drying for 24 hours to obtain imidazolyl ionic liquid (1-N-hexyl-3-methylimidazolium bromide ionic liquid [ HMIM ] Br), wherein the yield is about 85%;
secondly, 5g of KMnO4Gradually added to 50mL of concentrated H cooled in an ice bath2SO4And 5g of graphite foilTo the mixture of tablets (to maintain the temperature in the range of 0-10 ℃), followed by magnetic stirring at 50 ℃ for 0.5H, slow addition of 80 mL of distilled water, stirring the mixture at 95 ℃ for a further 10 min, addition of 200mL of distilled water and 15mL of 30% H by mass fraction2O2Then, the reaction mixture was centrifuged at 5000 rpm, and the centrifuged sediment was dispersed in 500mL of HCl having a mass fraction of 10%, and then the dispersion was centrifuged;
fourthly, repeating the third step for 3 times until the pH value of the supernatant is 5, and then collecting the graphene oxide from a centrifugal machine and drying the graphene oxide in vacuum at the temperature of 60 ℃ to obtain the graphene oxide;
fifthly, oxidizing the single-walled carbon nanotube in 400 ℃ air atmosphere for 2h in sequence, then acidifying the single-walled carbon nanotube for 24h by using concentrated hydrochloric acid to obtain a primary purified product of SWNTs, putting 100mg of the primarily purified SWNTs into a 250mL plastic beaker, adding 150mL of potassium peroxodisulfate solution with the concentration of 0.2mol/L, performing ultrasonic crushing and dispersion for 1h at 10 ℃, adding 12.5mL of concentrated sulfuric acid with the mass fraction of 97% into the reaction system, performing magnetic stirring and refluxing in an oil bath at 60 ℃ for 24h, finishing the reaction, after the system is cooled, removing an upper yellow solution, pouring and dispersing a lower black component for multiple times until a stable suspension is formed, finally performing suction filtration on the suspension by using a 1 micron PTFE filter membrane, and performing vacuum drying on the obtained filter cake for 8h at 100 ℃ to obtain the single-walled carbon nanotube;
sixthly, respectively taking 1mg of graphene oxide and the oxidized single-walled carbon nanotube, respectively placing the graphene oxide and the oxidized single-walled carbon nanotube into 100mL of imidazolyl ionic liquid with the mass fraction of 1%, and performing ultrasonic crushing and dispersion to respectively obtain a graphene oxide dispersion liquid and a dispersion liquid of the oxidized single-walled carbon nanotube;
and seventhly, adding the equal-volume graphene oxide dispersion liquid and the dispersion liquid of the oxidized single-walled carbon nanotube into the PTFE liner, adjusting the pH value of the mixed liquid to 9 by using dilute ammonia water with the concentration of 2mol/L, then putting the PTFE liner into a reaction kettle to be screwed, putting the PTFE liner into a forced air drying oven to be dried for 12 hours at the temperature of 60 ℃, then putting the PTFE liner into a semipermeable membrane to carry out ion exchange purification, carrying out suction filtration, and freezing for 36 hours at the temperature of-25 ℃ in a vacuum drying oven to obtain the graphene carbon nanotube aerogel composite material.
Experiment three:
the preparation method of the graphene carbon nanotube composite aerogel electrode material comprises the following steps:
firstly, mixing 1-bromoethane and N-methylimidazole according to the mass ratio of 1: 2, magnetically stirring for 24 hours at 60 ℃ in an oil bath, pouring out supernatant, adding ethyl acetate into the generated viscous product for washing, fully stirring, pouring out supernatant, adding acetonitrile into the washed crude product, heating to dissolve an intermediate, repeating the washing steps until a clear and transparent viscous product is obtained, and placing the viscous product in a vacuum drying oven at 60 ℃ for drying for 24 hours to obtain imidazolyl ionic liquid ([ EMIM ] Br), wherein the yield is about 85%;
secondly, 5g of KMnO4Gradually added to 50mL of concentrated H cooled in an ice bath2SO4And 5g of graphite flakes (to maintain the temperature in the range of 0-10 ℃), followed by magnetic stirring at 50 ℃ for 0.5H, slow addition of 80 mL of distilled water, stirring the mixture at 95 ℃ for a further 10 min, addition of 200mL of distilled water and 15mL of H with a mass fraction of 30%2O2Then, the reaction mixture was centrifuged at 5000 rpm, and the centrifuged sediment was dispersed in 500mL of HCl having a mass fraction of 10%, and then the dispersion was centrifuged;
fourthly, repeating the third step for 3 times until the pH value of the supernatant is 5, and then collecting the graphene oxide from a centrifugal machine and drying the graphene oxide in vacuum at the temperature of 60 ℃ to obtain the graphene oxide;
fifthly, oxidizing the single-walled carbon nanotube in 400 ℃ air atmosphere for 2h in sequence, then acidifying the single-walled carbon nanotube for 24h by using concentrated hydrochloric acid to obtain a primary purified product of SWNTs, putting 100mg of the primarily purified SWNTs into a 250mL plastic beaker, adding 150mL of potassium peroxodisulfate solution with the concentration of 0.2mol/L, performing ultrasonic crushing and dispersion for 1h at 10 ℃, adding 12.5mL of concentrated sulfuric acid with the mass fraction of 97% into the reaction system, performing magnetic stirring and refluxing in an oil bath at 60 ℃ for 24h, finishing the reaction, after the system is cooled, removing an upper yellow solution, pouring and dispersing a lower black component for multiple times until a stable suspension is formed, finally performing suction filtration on the suspension by using a 1 micron PTFE filter membrane, and performing vacuum drying on the obtained filter cake for 8h at 100 ℃ to obtain the single-walled carbon nanotube;
sixthly, respectively taking 1mg of graphene oxide and the oxidized single-walled carbon nanotube, respectively placing the graphene oxide and the oxidized single-walled carbon nanotube into 100mL of imidazolyl ionic liquid with the mass fraction of 1%, and performing ultrasonic crushing and dispersion to respectively obtain a graphene oxide dispersion liquid and a dispersion liquid of the oxidized single-walled carbon nanotube;
and seventhly, adding the equal-volume graphene oxide dispersion liquid and the dispersion liquid of the oxidized single-walled carbon nanotube into the PTFE liner, adjusting the pH value of the mixed liquid to 10 by using dilute ammonia water with the concentration of 2mol/L, then putting the PTFE liner into a reaction kettle to be screwed, putting the PTFE liner into a blast drying oven to be dried for 12 hours at the temperature of 60 ℃, then putting the PTFE liner into a semipermeable membrane to carry out ion exchange purification, carrying out suction filtration, and freezing for 36 hours at the temperature of-25 ℃ in a vacuum drying oven to obtain the graphene carbon nanotube aerogel composite material.
Experiment four:
the preparation method of the graphene carbon nanotube composite aerogel electrode material comprises the following steps:
firstly, mixing 1-bromo-N-octane and N-methylimidazole according to the mass ratio of 1: 2, magnetically stirring for 24 hours under a 60 ℃ oil bath, pouring out supernatant, adding ethyl acetate into the generated viscous product for washing, fully stirring, pouring out supernatant, adding acetonitrile into the washed crude product, heating to dissolve an intermediate, repeating the washing steps until a clear and transparent viscous product is obtained, and placing the viscous product in a 60 ℃ vacuum drying oven for drying for 24 hours to obtain imidazolyl ionic liquid ([ OMIM ] Br), wherein the yield is about 85%;
secondly, 5g of KMnO4Gradually added to 50mL of concentrated H cooled in an ice bath2SO4And 5g of graphite flakes (to maintain the temperature in the range of 0-10 ℃), followed by magnetic stirring at 50 ℃ for 0.5H, slow addition of 80 mL of distilled water, stirring the mixture at 95 ℃ for a further 10 min, addition of 200mL of distilled water and 15mL of H with a mass fraction of 30%2O2Then, the reaction mixture was centrifuged at 5000 rpm, and the centrifuged sediment was dispersed in 500mL of HCl having a mass fraction of 10%, and then the dispersion was centrifuged;
fourthly, repeating the third step for 3 times until the pH value of the supernatant is 5, and then collecting the graphene oxide from a centrifugal machine and drying the graphene oxide in vacuum at the temperature of 60 ℃ to obtain the graphene oxide;
fifthly, oxidizing the single-walled carbon nanotube in 400 ℃ air atmosphere for 2h in sequence, then acidifying the single-walled carbon nanotube for 24h by using concentrated hydrochloric acid to obtain a primary purified product of SWNTs, putting 100mg of the primarily purified SWNTs into a 250mL plastic beaker, adding 150mL of potassium peroxodisulfate solution with the concentration of 0.2mol/L, performing ultrasonic crushing and dispersion for 1h at 10 ℃, adding 12.5mL of concentrated sulfuric acid with the mass fraction of 97% into the reaction system, performing magnetic stirring and refluxing in an oil bath at 60 ℃ for 24h, finishing the reaction, after the system is cooled, removing an upper yellow solution, pouring and dispersing a lower black component for multiple times until a stable suspension is formed, finally performing suction filtration on the suspension by using a 1 micron PTFE filter membrane, and performing vacuum drying on the obtained filter cake for 8h at 100 ℃ to obtain the single-walled carbon nanotube;
sixthly, respectively taking 1mg of graphene oxide and the oxidized single-walled carbon nanotube, respectively placing the graphene oxide and the oxidized single-walled carbon nanotube into 100mL of imidazolyl ionic liquid with the mass fraction of 1%, and performing ultrasonic crushing and dispersion to respectively obtain a graphene oxide dispersion liquid and a dispersion liquid of the oxidized single-walled carbon nanotube;
and seventhly, adding the equal-volume graphene oxide dispersion liquid and the dispersion liquid of the oxidized single-walled carbon nanotube into the PTFE liner, adjusting the pH value of the mixed liquid to 10 by using dilute ammonia water with the concentration of 2mol/L, then putting the PTFE liner into a reaction kettle to be screwed, putting the PTFE liner into a blast drying oven to be dried for 12 hours at the temperature of 60 ℃, then putting the PTFE liner into a semipermeable membrane to carry out ion exchange purification, carrying out suction filtration, and freezing for 36 hours at the temperature of-25 ℃ in a vacuum drying oven to obtain the graphene carbon nanotube aerogel composite material.
Claims (10)
1. The preparation method of the graphene carbon nanotube composite aerogel electrode material is characterized by comprising the following steps of:
mixing 1-bromo-N-alkane and N-methylimidazole, magnetically stirring for 24 hours at 60 ℃ in an oil bath, pouring out supernatant, adding ethyl acetate into the generated viscous product for washing, fully stirring, pouring out the supernatant, adding acetonitrile into the washed crude product, heating to dissolve an intermediate, repeating the washing steps until a clear and transparent viscous product is obtained, and placing the viscous product in a vacuum drying oven at 60 ℃ for drying for 24 hours to obtain imidazolyl ionic liquid;
wherein the mass ratio of the N-methylimidazole, the 1-bromo-N-alkane, the acetonitrile and the ethyl acetate is 1-5: 5-10: any;
secondly, 5-10 g of KMnO4Gradually adding 50-100 mL of concentrated H cooled in an ice bath2SO4And 1-10 g of graphite flakes, then magnetically stirring for 0.5-1 h at 50 ℃, slowly adding 50-100 mL of distilled water, and stirring the mixture for 10-30 minutes at 95 ℃;
thirdly, sequentially adding 200-300 mL of distilled water and 10-30 mL of H with the mass fraction of 30% into the product obtained in the second step2O2Centrifuging the reaction mixture at the speed of 5000 rpm, dispersing the centrifuged sediment in 300-500 mL of HCl with the mass fraction of 10%, and centrifuging the dispersion;
fourthly, repeating the third step for 3 times until the pH value of the supernatant is 5-7, and then collecting the graphene oxide from a centrifugal machine and drying the graphene oxide in vacuum at the temperature of 60 ℃ to obtain the graphene oxide;
fifthly, oxidizing the single-walled carbon nanotube in 400 ℃ air atmosphere for 2h in sequence, then acidifying the single-walled carbon nanotube for 24h by using concentrated hydrochloric acid to obtain a primary purified product of SWNTs, taking 100-200 mg of the primarily purified SWNTs, adding 150-200 mL of potassium peroxodisulfate solution with the concentration of 0.2mol/L, ultrasonically crushing and dispersing for 1-2 h at 10 ℃, adding 12.5-15 mL of concentrated sulfuric acid with the mass fraction of 97% into the reaction system, placing the reaction system in an oil bath at 60 ℃ for magnetic stirring and refluxing for 24-36 h, after the reaction is finished, removing the upper yellow solution after the system is cooled, pouring and dispersing the lower black component for multiple times until a stable suspension is formed, finally performing suction filtration on the suspension by using a 1 micron PTFE filter membrane, and placing the obtained filter cake in vacuum drying for 8h at 100 ℃ to obtain the oxidized single-walled carbon nanotube;
sixthly, respectively taking 1mg of graphene oxide and the oxidized single-walled carbon nanotube, respectively placing the graphene oxide and the oxidized single-walled carbon nanotube into 100mL of imidazolyl ionic liquid with the mass fraction of 1-2%, and performing ultrasonic crushing and dispersion to respectively obtain a graphene oxide dispersion liquid and a dispersion liquid of the oxidized single-walled carbon nanotube;
and seventhly, adding the equal-volume graphene oxide dispersion liquid and the dispersion liquid of the oxidized single-walled carbon nanotube into the PTFE liner, adjusting the pH value of the mixed liquid to 8-13 by using dilute ammonia water with the concentration of 2-5 mol/L, putting the PTFE liner into a reaction kettle, screwing down, putting the PTFE liner into a blast drying oven, drying for 1-24 hours at the temperature of 60 ℃, then putting the PTFE liner into a semipermeable membrane for ion exchange purification and suction filtration, and freezing for 36-48 hours at the temperature of-25 ℃ to obtain the graphene carbon nanotube aerogel composite material.
2. The preparation method of the graphene-carbon nanotube composite aerogel electrode material according to claim 1, wherein the 1-bromo n-alkane in the first step is 1-bromo n-ethane, 1-bromo n-butane, 1-bromo n-hexane, 1-bromo n-octane or 1-bromo n-decane.
3. The method for preparing the graphene-carbon nanotube composite aerogel electrode material as claimed in claim 1, wherein the concentrated H in the second step2SO4The concentration is 98%, 80% or 70%.
4. The preparation method of the graphene carbon nanotube composite aerogel electrode material as claimed in claim 1, wherein in the second step, 6-8 g of KMnO is added4Gradually adding the mixture into 60-80 mL of concentrated H cooled in an ice bath2SO4And 2-4 g of graphite flakes.
5. The preparation method of the graphene carbon nanotube composite aerogel electrode material as claimed in claim 1, wherein the mixture is stirred at 95 ℃ for 15-25 minutes in the second step, and 200-300 mL of distilled water and 15-25 mL of 30% H are sequentially added2O2Thereafter, the reaction mixture was centrifuged at 5000 rpm.
6. The preparation method of the graphene carbon nanotube composite aerogel electrode material as claimed in claim 1, wherein the preparation method is characterized in thatIn the second step, the mixture is stirred for 20 minutes at 95 ℃, and 200mL to 300 mL of distilled water and 20 mL of H with the mass fraction of 30 percent are added in turn2O2Thereafter, the reaction mixture was centrifuged at 5000 rpm.
7. The method for preparing the graphene carbon nanotube composite aerogel electrode material according to claim 1, wherein the pH value of the supernatant in the fourth step is 6.
8. The preparation method of the graphene carbon nanotube composite aerogel electrode material according to claim 1, wherein 150mg of primarily purified SWNTs are taken in the fifth step, 160mL of potassium peroxodisulfate solution with the concentration of 0.2mol/L is added, ultrasonic crushing and dispersion are carried out for 1-2 h at 10 ℃, and 13mL of concentrated sulfuric acid with the mass fraction of 97% is added into the reaction system.
9. The method for preparing the graphene carbon nanotube composite aerogel electrode material as claimed in claim 1, wherein the pH of the mixed solution is adjusted to 10 in the seventh step.
10. The preparation method of the graphene carbon nanotube composite aerogel electrode material as claimed in claim 1, wherein the step seven is performed by freezing at-25 ℃ for 40 h.
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